Treatment of hydrocarbons



Aug. 31, 1937. G. EGLOFF TREATMENT OF HYDROCARBONS original Filed Dec. 14. 1931 rotating cylindrical shell I Il adapted to rotate in fixed heads II and I3. Means are indicated in trunnion I5 driven by power means not shown and gear I6 ilxed on shell III for rotating the shell at controllable ratesof speed. To prevent leakage when operations are conducted under superatmospheric pressures, multiple packing rings indicated by I2 and I4 are provided,'and in addition to such devices special oil sealed pres- 10 sure rings and the like may be employed. There may also be present means for continuously transferring solid accumulations of coke toward the lower or discharge end of the reaction chamber such as, for example, a fixed internal shaft supported at either end on the two stationary heads II and I3, the shaft in turn supporting curved blades or hobs which work the material toward the discharge end during the rotation of the'shell and insure the continuous removal of gosuch deposits. Since other means such as loose steel balls, chains, etc. may be employed in a similar manner and since such means do .not constitute an essential part of the present invention, no particular means has been indicated inthe drawing.

The reaction zone may be exteriorly heated by hot combustion gases produced in a combustion zone 54, which forms a part of a furnace setting 51 having a perforated arch 56 between combustion zone and the heating zone 55 to prevent the direct impingement of combustion gases upon the reaction chamber and a proper outlet 63 for the exit of combustion gases to a suitable stack not shown. Fuel may be supplied to a burner..

53 from a line 5I controlled` by a valve 52 and gases such as steam or air for atomizing the fuel may be admitted from a line 49 controlled by a valve 50. The solid carbonaceous residues produced in '.the reaction zone are preferably discharged through a line I1 of sufficient diameterv to readily accommodate the size of the lumps, this line being integral with lower fixed head I3 and branching into lines I8 and I9 leading respectively to coke receivers 26 and 21 which are preferably maintained under process pressure while receiving coke. To enable the continuous discharge of coke under pressure, slide valves 20' and 2| are provided in lines I8 and I9 respecever pressure may be employed in ythe reaction zone and enable the alternate use of the coke receivers, one being filled 'with coke while the other is being cleaned, the pressure having been released prior to cleaning. The controllable removal of coke to the receivers may be effected by such means as is indicated by the screw conveyors 22 and 23 in lines I3 and I9, rotated by power means 24 and y25 respectively. Receivers sure coke receivers in parallel may be provided with vent lines 28 and 30 containing valves 29 and 3Irespectively and also tight doors 32 and rangement of apparatus which may be employed,

to segregate vapors of desired boiling rangefrom liquids amenable to further heat treatment and the gases and vapors may pass through a line 31 controlled by a valve 38 and be cooled by a condenser 39, the cooled products passing through a line 40 controlled by. a. valve 4I to a receiver tively, these valves being designed to hold what- 26 and 21, which typify any arrangement of pres- 33 which can be removed to permit access to the 42. Such a receiver may be provided with a.

' gas line 43 controlled by a valve 44 and a liquid withdrawal line 45 controlled by a valve 46- for the removal of process liquids. Heavy rei'luxes accumulating in the fractionator may pass through a line 41 controlled. by a valve 48 to a pump 58 which discharges into a line 59 conftrolled by a valve 60. A branch line 6I leading conversion.' such portions as are not desired for further processing being withdrawn to suitable storage through valve 60 in line 59.

The reaction chamber has been indicated in the drawing as being at a relatively slight angle with the horizontal-but it is within the scope of the invention to vary this angle when necessary to adapt the process tov different types of coaloil mixtures which may be employed in the decomposition reactions which are brought about. In the majority of cases the amount of coke deposited during the passage of materials through the rotating chamber will' increase toward the discharge end and it may at times be only necessary to provide scraping devices in the lower portion of the shell. In some instances also such devices may not be necessary as, for example, when large amounts of low volatile coal are employed in the charging mixture.

It is characteristic of the process of the invention that means are provided for the continuous removal of coke deposits formed by the cracking of coke oil mixtures under elevated temperatures and pressures. It is not intended to confine the invention to the cracking or pyrolysis of such mixtures to produce mainly coke and motor fuel but it is intended to include the manufacture Iof major amounts of fuel gases by utilizing mixtures'of steam and air in the heating and conversion zones and on the other hand to include the use of reducing or hydrogenating gases in thepresence of catalytic materials' `to produce maximum or optimum yields of liquid products under hydrogenating conditions. The means shown for exteriorly heating the rotating shell ofthe reaction chamber enable Vthe employment of temperatures higher than those produced n the initial heating zone if necessary to the objects desired. In thecase of conversion under hydrogenating conditions, it may sometimes be necessary lto cool the reaction zone instead of heating it since the classes of reactions men. tioned are characteristically exothermic.

In the matter of temperatures and pressures, any temperature found suitable for the particular object in view, either gas manufacture, motor fuel production or hydrogenation, may be employed and correspondingly the pressures necessary for successful operation of these types of processes.

Catalytic reagents may be employed in the reaction zone, particularly in the case that the process is utilized for hydrogenation, examples of such catalytic'materials being Such metals and oxides of the same as' nickel, cobalt, iron, 'vanadium, tungsten, molybdenum, etc. and their oxides and sulfides either alone or in combination.

As an example'of an operation which may be' conducted within the scope of the invention and thev results obtainable therefrom, mention may bemade of a case wherein a 40%,suspension of iinely divided coalin oil is treated. The oil may be.a 24 A. P. I. gravity straight run rsiduum produced by the topping of lVIid-Continent crude oil .and the coal may be of a bituminous character containing 30% volatile matter by analysis. The mixture may be processed using a temperature at i, the exit of the heating element of 875 F. and a pressure at this point and throughout the reaction chamber and succeeding equipment of substantially 200 lbs. per sq. in. 'I'he retort may be exteriorly heated to maintain a mean tempera- 10 ture of approximately 1050 F. therein.

As a result of this processing there may be produced from a barrel of material charged 22 gals.

of a hydrocarbon mixture of the approximately boiling point range of commercial motor fuel, l 150 lbs. of coke of 5-10% volatile matter and 1400 cu. ft. of gas having a specific gravity referred to air of 0.6 and a heating value of. 900 B. t. u. per cu. ft. 'Ihe gasoline, owing prin-n cipally to its content of aromatic hydrocarbons 2'0 produced in the cracking of the coal, may have a high antiknock value equivalent of 50 to 60% benzol. Owing to the return of the reflux from the fractionating column to the heating element the process may be so conducted that Ano other 25 liquids other than the motor fuel are produced. In addition, owing to the means provided for the continuous removal of coke, such an operation may be conducted over a period of from one to two weeks without shutdown.

30 When introducing approximately 8% of hydrogen by weight of coal and oil mixture undergoing treatment in the proportions shown in the aforementioned example employing a mixture of. 24 A. P. I. gravity straight run residuum and 35 bituminous coal and under conditions of treat-v per cubic foot for each barrel of the oil and coal l mixture charged may be produced. The sulphur content of the distillate may alsobe reduced considerably by this treatment.

50 When introducing approximately 12% of air into the retort wherein the coal and oil mixture are undergoing treatment employing a transfer temperature of approximately 800 F. and a temperature within the retort `of approximately 55 1050 F. maintaining substantially atmospheric pressure on the retort and the succeeding elements of the system and a pressure upon the heating element of approximately 200 pounds per square inch, the yield of materialy boiling 60 within motor fuel boiling range may be approxv imately 23 gals. per barrel of material charged making in addition to the motor fuel product approximately 130 pounds of coke of low volatile matter and approximately 1500y cubic feet of gas having a heating value of. approximately 850 B.

t. u. per cubic foot. The gasoline may contain .substantial percentages of oxidation products which increase the antiknock value over that of' the product produced when air is not introduced 70 into the retort of approximately 8 points in octane value or approximately 15 points in benzol value` The 'foregoing description and example have served to indicate that the process of the inven# tion is broad in scope and applicable to a wide variety of charging mixes and consequently the description and examples are not to be construed in a limiting sense but as illustrative merely.

I claim as my invention:

1. A process for recovering hydrocarbon liquids of motor'fuel like character from hydrocarbon containing solids and liquids comprising mixing with a relatively heavy hydrocarbon liquid suitable proportions of a finely comminuted hydrocarbon containing solid to form a free flowing fluid mixture, subjecting the resultant mixture to a cracking temperature while ow'lng in a stream'through a heating zone, discharging the heated mixture into an elongated rotary coking zone, introducing hydrogen to the mixture in the coking zone, maintaining the mixture in the presence of the hydrogen at a conversion temperature for the requisite time period to complete conversion, distilling the mixture to coke in the coking zone, subjecting vapors evolved from the mixture to reflux condensation and re- .turning the resulting reflux for further treatment to the heating zone, condensing the vapors escaping reflux condensation and collecting the resulting distillate.

A process for recovering hydrocarbon liqui s of motor fuel like character from hydro;- carbon containing solids and liquids comprising mixing with a relatively heavy hydrocarbon liquid suitable proportions'of a nely comminuted hydrocarbon containing solid to form a free flowing fluid mixture, heating the resultant mixture to cracking temperature while flowing in a restricted stream through a heating zone, discharging the heated mixture into an enlarged rotating hydrogenating zone, introducing hydrogen to the mixture in said rotating zone, maintaining the mixture in the presence of the hydrogen under hydrogenating conditions of temiperature and pressure for a sufficient time to effect substantial conversion thereof into lower q boiling products, subjecting vapors evolved from themixture to` fractionation and returning resultant reflux condensate to the heating-zone. and finally condensing and/collecting the fractionated vapors. q

3. A process for recovering hydrocarbonvliquids of motor fuel like character from hydrocarbon containing solids and liquids comprising mixing with a relatively heavy hydrocarbon liquid suitable proportions of a finelycomminuted hydrocarbon containing solid to from a free owing fluid mixture, heating the resultant mixture to cracking temperature *while flowing in a restricted stream through a heating zone, discharging the heated mixture into an enlarged rotating hydrogenating zone, introducing hydrogen to the mixture in said rotating zone, maintaining the mixture in the presence of the hydrogen under hydrogenating conditions of temperature and pressure for a sufficient time to effect substantial conversion thereof into lower boiling products, and recovering lower boiling products thus produced.

- GUSTAV EGLOFF. 

